Mineral oil composition



Patented Jan. 11, 1949 UNITED STATES PATENT OFFICE MINERAL OILCOMPOSITION Edward A. Oberright, Woodbury,..-N. J asslgnor toSocony-Vacuum Oil Company, Incorporated, a corporation of New York NoDrawing. Application July 6, 1945, Serial No. 603,590

13 Claims. (Cl. 252-3237) ous uses are in and of themselves usuallydefi.-'

cient in one or more respects so that their practical utility is limitedeven in the particular field for which they have been refined. Forexample, mineral oil fractions refined'for use as lubricants have atendency to oxidize under conditions of use, with the formation ofsludge or acidic oxidation products; also, the lighter fractions such asgasoline and kerosene tend to oxidize with the formation of colorbodies, gum, etc. In order to prevent the formation of these-productsand thereby extend the useful life of the oil fraction, it is commonpractice to blend with such oil fraction an additive ingredient whichwill inhibit oxidation, such ingredients being known to the trade\asoxidation inhibitors, antioxidants,

sludge inhibitors, gum inhibitors, etc. 7

It is also the practice to add other ingredients to mineral oilfractions for the purpose of improving oiliness characteristics and thewearreducing actionof such mineral oils when they are used aslubricants, particularly when the oils are used for the purpose oflubricating metal surfaces which are engaged under extremely highpressures and at high rubbing speeds.

Various other ingredients have been developed for the purpose ofdepressing the pour point of mineral oil fractions which have beenrefined for use as lubricants.- Most refining treatments provide oilscontaining a small amount of wax which,-without the added ingredient,would tend to crystallize at temperatures which render the oilimpracticable for use under low temperature conditions. Additive agentshave also been developed for improving the viscosity index of lubrieating oil fractions. In the case of internal combustion engines,particularly those operating with high cylinder pressures, there is adecided tendency for the ordinary lubricating oil fractions to formcarbonaceous deposits which cause the piston rings to become stuck intheir slots and which fill the slots in the oil ring or rings, thusmate- It has also been discovered that certain types of recentlydeveloped hard metal alloys, such as cadmium-silver alloy bearings, areattacked by ingredients in certain types of oils, particularly oils ofhigh viscosity index obtained by various methods of solvent-refining.This corrosive action on such alloys has led to the development 01corrosion-inhibitors which may be used in solvent-refined oils toprotect such bearing metals against this corrosive action. I

In the lighter mineral oil fractions, such as those used for fuelpurposes, particularly in internal combustion engines, it has been foundthat the combustion characteristics of the fuel may be controlled andimproved by adding minor proportions of various improving agentsthereto.

'The various ingredients which have been developed for use in mineraloil fractions to improve such fractions in the several characteristicsenumerated above are largely specific to their particular applications.Therefore, it has been the practice to add a separate ingredient foreach of the improvements which is to be effected.

The present invention is predicated upon the discovery of a group orclass of-oil-soluble reaction products or compounds which, when added tomineral oil fractions in minor proportions, will improve the oilfractions in several respects.

The novel addition agents contemplated by this invention asmultifunctional improvers for mineral oils are oil-solublephosphorus-containing and phosphorusand sulfur-containing reactionproducts obtained by reacting an aldehyde, a hydroxyaromatic compoundand a polyamine in which each amino group is characterized by thepresence of at least one hydrogen atom to form a condensation productand thereafter reacting the latter with either: a phosphorus halide to'fur-containing reaction product. Preferred phosphorus-containingreaction products are those obtained by condensing about one molarequivalent of an aldehyde with at least one-half molar equivalent of apolyamine of the aforesaid character and with a quantity of analkyl-substituted hydroxyaromatic compound suflicient that the contentof the ,hydroxyaromatic substituent is about one molar equivalent,followed by reaction with at least one molar equivalent of a phosphorushalide. Similarly, preferred phosphorusand sulfur-containing reactionproducts are those obtained by reacting a condensation product of theaforesaid preferred type with either a phosphorus sulfide, or aphosphorus halide and a sulfur halide. Metal salts of thesephosphorus-containing and phosphorusand sulfur-containing reactionproducts are also contemplated herein.

Aldehydes contemplated by the present invention are the aliphaticaldehydes, typified by formaldehyde (such as trioxymethylene),acetaldehyde, and aldol (p-hydroxy butyraldehyde); aromatic aldehydes,representative of which is benzaldehyde; heterocyclic aldehydes, such asfurfural; etc. The aldehyde may contain a substituent group such ashydroxyl, halogen, nitro and the like; in short, any substituent whichdoes not take a major part in the reaction. Preference, however, isgiven to the aliphatic aldehydes, formaldehyde being particularlypreferred.

The polyamines contemplated herein are those in which each amino groupis characterized by the presence of at least one hydrogen atom. Suchpolyamines may contain only primary amino groups, only secondary aminogroups, or both primary and secondary groups. Typical polyamines are thealiphatic homologs, ethylene diamine, propylene diamine, polyalkenepolyamines (e. g..

diethylene triamine, triethylene tetramine); the v aromatic homologs,mand p-phenylene diamine, diamino naphthalenes, etc. Of this class ofamines, preference is given to the diamines in which two primary aminogroups are attached to adjacent carbon atoms, and particular preferenceis accorded ethylene diamine.

Representative hydroxyaromatic compounds contemplated by the presentinvention are phenol, resorcinol, hydroquinone, catechol, cresol,xylenol, hydroxydiphenyl, benzylphenol, phenylethylphenol, phenolresins, methylhydroxydiphenyl, guiacol, alpha and beta naphthol, alphaand beta methylnaphthol, tolylynaphthol, xylyinaphthol, benzylnaphthol,anthranol, phenyl'methylnaphthol, phenanthrol, monomethyl ether ofcatechol, phenoxyphenol, chlorphenol, and the like. Preference ingeneral is to the monohydroxy phenols otherwise unsubstituted,particular preference being given to phenol and alpha and beta naphthol.The hydroxyaromatic compounds may also contain one or more substituentgroups such as carboxyl, halogen, nitro and the like; here again,

any substituent may be present which does not take a predominant part inthe condensation with the aldehyde and the polyamine. Preferred of suchsubstituents is a carboxyl group.

As indicated hereinabove, the hydroxyaromatic compound may contain oneor more alkyl substituents such as short-chain groups, typified bymethyl, ethyl, amyl, etc. or long-chain, relativelyhigh-molecular-weighthydrocarbon groups having at least twenty carbon atoms, typified byalkyl groups derived from petroleum wax, which is a predominantlystraight-chain aliphatic hydrocarbon of at least twenty carbon atoms. Itwill be obvious to those skilled in the art that the maximum number ofalkyl groups is limited the nucleus is mono-.or poly-cyclic and as thenucleus is otherwise substituted, with such groups as carboxy, nitro,amino, halogen and the like.

The present application has been purposely directed to condensationproducts of the aforesaid reactants for, as yet, the theory of reactionis not fully understood. Some evidence is available-for example,quantitative analysis of the reaction product-to point to the presenceof a major quantity of one compound. For instance, when typicalreactants, such as an alkyl-substituted phenol, formaldehyde andethylene diamine, are reacted as hereinafter described, analysisindicates that the predominant product is: r

HO OH H H H H H H Hat-Antiit H 1 it wherein R is an alkyl group.

Probably also present in the condensation product are compounds of thefollowing type:

and v R s 1-; R H0 1 on i z a A R It will be apparent, therefore, thatwhen the condensation product is reacted with a phosphorus compound ofthe foregoing type, or with such a compound and a sulfurizing material,the reaction product obtained thereby is of greater chemical complexity.For this reason, it will be clear that the foregoing is for illustrativepurposes only and is not to be construed as limiting the presentinvention to a theory of reaction because the present invention isdirected primarily to condensation products obtained by inter-reactionof the reactants described herein as multi-functional improving agentsfor lubricating oils and the like.

In preparing the intermediate or condensation products contemplatedherein, the reactants may be added to each other in any order. A typicalprocedure involves adding the aldehyde to an alcohol solution of thehydroxyaromatic compound and the amine. The reaction may also be carriedout in the presence of other diluents or solvents such, for example, astetrachlorethane. chlorbenzene, mineral oil, etc. In the event thatmineral oil is used as a diluent, the mineral oil may be retained,rather than separated from the reaction product, thereby providing amineral oil concentrate.

The reaction temperature may be varied conthe solvent for an additionalperiod of several hours.

The reaction product may be water washed to assure complete removal ofany unreacted amine and this is recommended when the amine is highboiling. When an alcohol is used as a diluent in the reaction, it isdistilled from the reaction mixture, thereby also removing any unreactedamine and water of reaction or water added with the reactants (Formalin,for example, is generally used in a 37% aqueous solution.)

As stated above, the general procedure for preparing the contemplatedcondensation products involves the inter-reaction of a hydroxyaromaticcompound, an aliphatic aldehyde, and a polyamine wherein the aminogroups have at least one free hydrogen.

A typical, and also preferred, alkyl-substituted hydroxyaromaticcompound which may be used is a wax-substituted phenol, wax-phenol." Theterm wax as used herein designates petroleum wax or aliphatichydrocarbons or hydrocarbon groups of the type which characterizepetroleum wax. These so-called wax" substituents may be obtained byalkylation of the phenol or hydroxyaromatic hydrocarbon with arelativelyhigh-molecular weight aliphatic hydrocarbon or mixture of suchhydrocarbons (such as petroleum wax) by any suitable alkylationprocedure such, for example, as by a Friedel-Crafts condensation ofchlorinated petroleum wax with phenol.

As indicated hereinabove, the reaction products contemplated herein maybe prepared by reacting a condensation product of the type describedabove with a phosphorus halide, a phosphorus sulfide or thiohalide, orat least one such phosphorus compound and a sulfurizing material. Thisreaction is preferably carried out in the presence of an inert diluentsuch as tetrachlorethane, benzene, chlorbenzene, mineral oil, etc. Thesediluentsexcept heavy mineral oils-are removed after the reaction bydistillation of the reaction mixture which contains the desired reactionproduct. When a mineral oil is used as the diluent, however, it may beretained, thereby providing a mineral oil concentrate containing thereaction product.

The reaction temperature may be varied considerably, depending upon thereaction time and the specific phosphorus, and/or sulfur, reactant used.Temperatures of the order of about C. to about 200 C. are generallymaintained with a phosphorus halide. The preferred procedure, however,involves adding a phosphorus halide to a condensation product at roomtemperature (20- C.) and thereafter heating the reaction mixture soformed at the reflux temperature of the diluent for several hours.Related phosphorusand sulfur-containing reaction products, in general,are also prepared under the foregoing conare elementary sulfur, sulfurhalides and mixtures thereof. 01' these materials, sulfur halides arepreferred, with sulfur monochloride particularly preferred.

Metal salts, of the aforesaid phosphorusand phosphorusand sulfur-,containing reaction products, as indicated above, also fall within thescope of the present invention.- Any metal may be used the oxide orhydroxide of which (in alcohol solution, if necessary) can be reactedwith the intermediate condensation product, or a salt of which can bereacted in alcohol solution with the sodium salt of the intermediateproduct. Among the metals contemplated forthis purpose are copper,beryllium, magnesium, calcium, strontium, barium, radium, zinc, cadmium,mercury, germanium, tin, lead, vanadium, chromium, manganese, iron,cobalt, nickel, ruthenium, palladium, platinum, aluminum, antimony,arsenic, bismuth, cerium, columbium, gallium, gold, in-

dium,-iridium, molybdenum, osmium, rubidium,-

selenium, tantalum, tellurium, thorium, titanium, tungsten, uranium, andzirconium. Preference is given to metals of the alkaline earth group,particularly to barium. As noted above, the metal is preferablyintroduced by reaction of its oxide or hydroxide with the intermediatecondensation product. Where necessary, an alcohol solution of the oxideor hydroxide is used. The metal salts can also be prepared by reactingthe sodium salt of the intermediate product with an alcohol solution ofa salt of the desired metal, such as stannous chloride, lead acetate,thorium nitrate, titanium tetrachloride, etc.

Details of a preferred procedure for making the condensation products ofthis invention where the. aforesaid wax-phenol is employed as thealkyl-substituted hydroxyaromatic compound may be obtained from thefollowing examples:

EXAMPLE I A. Alkylation of phenol A paramn wax melting at approximatelyF. and predominantly comprised of compounds having at least twentycarbon atoms in their molecules is melted and heated to aboutv 200 F.,

after which chlorine is bubbled therethrough unwax thus obtained,containing two atomic pro-- portions of chlorine, is heated to atemperature varying from just above its melting point to not over F.,and one mol of phenol (CcHaOI-I is admixed therewith. The mixture isheated to about150 F., and a quantity of anhydrous aluminum chloridecorresponding to about 3 percent of the weight of chlor-wax in themixture is slowly added with active stirring. The rate of addition ofthe aluminum chloride should be suificiently slow to avoid violentfoaming, and during such addition the temperature should be held atabout 150 F. After the aluminum chloride has been added, the temperatureof the mixture may be increased slowly over a period of from 15 to 25minutes to a temperature of about 250 F. and then should be more slowlyincreased to about 350 F. To control the evolution of 1101 gas thetemperature of the mixture ispreterably raised from 250 F. to 350 F., ata rate of approximately one degree per minute, the whole heatingoperation occupying approximately two hours from the time of adding thealuminum chloride. If the emission of HCl gas has not ceased when thefinal temperature is reached, the mixture may be held at 350 F. for ashort time to allow completion of the reaction. However, to avoidpossible cracking of the wax, the mixture should not be heatedappreciably above 350 F., nor should it be held at that temperature forany extended length of time.

It is important that all unreacted or non-alkylated hydroxy-aromatn:material (phenol) remaining after the alkylation reaction be removed.Such removal can be eifected generally by waterwashing, but it ispreferable to treat the waterwashed product with superheated steam,thereby insuring complete removal of the unreacted material andaccomplishing the drying of the product in the same operation.

A wax-substituted phenol prepared according to the above procedure inwhich a quantity of chlorwax containing two atomic proportions ofchlorine and having a chlorine content of 16 percent is reacted with 1mol of phenol will be hereinafter designated as wax-phenol (2-16)! B.Formation of condensation product reflux (about 110 C.) and, thereafter,water washed until the washings were neutral. The solvents, butylalcohol and benzene, were removed from the reaction product bydistillation of the latter to a maximum temperature of 175 C. at mms.pressure, thereby obtaining the condensation product.

C. Phosphorus-containing condensation product Seventy-five grams of thecondensation product obtained in B, above, were dissolved in 150 gramsof mineral oil having a S. U. V. of 65 seconds at 210 F., and benzol(400 cc.) was then added thereto. Phosphorus trichloride (5.05 grams)was added dropwise to the mineral oilbenzol solution at about 25 C., andthe reaction mixture so obtained was stirred for one hour at thistemperature. The reaction mixture was then stirred at reflux (80 C.)fortwo hours. and was washed with sodium acetate solution to remove anyhydrochloric acid complexes that might have formed in the reaction, bythe action of evolved HCl on the reaction product. Benzol was removed bydistillation to a maximum temperature of 175 C. at 10 mms. pressure,entrained we.

.ture of 175 C. at 10 mms. pressure.

ter also being removed. The nitrogenand phosphorus-containing reactionproduct (Product One) is a 1:2 blend in mineral oil.

EXAMPLE II STANNOUS SALT OF PHOSPHORUS1CONTAINING CONDENSATION PRODUCTA. Condensation product A condensation product was prepared from thefollowing materials in the manner described in Example One (B),above:

Grams Wax-phenol (2-14) 150 Formaldehyde (37% aqueous solution) 19.5Ethylene diamine (69% aqueous solution) 20.8 Butyl alcohol solvent.

B. Phosphorus-containing condensation product Twenty-five grams of thecondensation product obtained in A, above, was blended with grams ofmineral oil (S. U. V. of 65 seconds at 210 F.) and tetrachlorcthane wasadded thereto. PCl: (1.72 grams) was added thereto, while stirring at 75C., and the resulting reaction mixture was stirred and heated at C. fortwo hours. A quantity of sodium butylate containing 1.72 grams of sodiumwas then added, followed by 8.28 grams of stannous chloride. Thereaction mixture thus obtained was refluxed at C. for two hours and thenfiltered through "Hi-Flo" clay. Solventstetrachloroethane andbutylalcoholwere distilled from the reaction mixture by distilling thelatter to a maximum tempera- The mineral oil blend (113) thus obtainedcontains the tinand phosphorus-containing reaction product (ProductTwo).

EXAMPLE III A. Condensation product Ethylene diamine, 43 grams of a 70percent solution of the same in water, was added to 86 grams of Formalin(35% solution) while agitating and cooling the same during one hour.Diamylphenol, 234 grams, was added thereto. The reaction temperaturegradually increased to about 100 C. whereupon water was distilled fromthe reaction mixture. The reaction mixture was blown with nitrogen gasand then heated at C. for two hours. Benzol, 200 ccs., were added to thereaction mixture and the resulting reaction mixture was washed withwater until the washings were neutral. Benzol and water were removedfrom the water-washed reaction mixture by distilling the same to amaximum temperature of C. at 5 mmsupressure. The condensation productthus obtained was diluted with mineral oil (S. U. V. of 65 seconds at210 F.) to form a 1:1 oil blend; the nitrogen content of the oil blendwas 2.78 percent.

B. Phosphorusand sulfur-containing reaction product Two hundred andseventy-six grams of condensation product (A) was mixed with 100 cc. ofbenzol. PCI: (12 grams) in 50 cc. of benzol was added dropwise at 25 C.during a period of one hour. S2C12 (1'? grams) in 50 cc. of benzol wasthen added thereto under the same conditions. The reaction mixture soobtained was then stirred at 25 C. for 3 hours and heated at reflux, 85C., for a similar period of time. The reaction mixture was washed withNaaCOa and thereafter was washed with water until the wash- 1118s wereneutral. The water-washed reaction mixture was distilled to a maximumtemperature EXAMPLEIV PHOSPHORUS- AND SULFUR-CONTAINING Rmc'rrorzPaonucr One hundred and thirty-eight grams of condensation product Three(A), in a 1:1 mineral oil blend, and 7 grams of P285 were heated for twohours at 150-l60 C. The reaction mixture was filtered through Hi-Flo ina steam-heated funnel under 10 mms. pressure. The filtrate (ProductFour) is a 1:1 011 blend containing 2.9 percent sulfur and 1.32 percentphosphorus.

Asstated hereinbefore, the reaction products contemplated by thisinvention and illustrated by the above examples, when added tolubricating oils in minor proportions, have been found to improve theseoils in several important respects. This phenomenon is demonstrated bythe following tables, which give the results of the various testsconducted to determine the effectiveness of these reaction products asaddition agents for lubricating oils. The percent of material added tothe oil in the following tables is the percent of concentrated materialand does not include the oil in which the product was made.

POUR Pom'r DEPRESSION Tests were conducted in the conventional mam herto determine the A. S. T. M. pour points of blends of these reactionproducts with a Mid- Continent solvent-refined oil of Saybolt UniversaiViscosity of 6'? seconds at'210 F. as compared with the pour point ofthe blank oil. The results given in Table I below demonstrate theeflectiveness of the reaction products contemplated herein as pour pointdepressants.

Table I A. s. 'r. M; Pour Point Values Addition Agent VrscosrrY IrmsxImaovamanr A mineral oil of 41.8 seconds Saybolt Universal viscosity at210 F. was tested in the conventional manner to determine theimprovement in viscosity index values effected by various of thereaction products contemplated by this inven-;

tion. This improvement is clearly demonstrated by the results set forthin Table II below.

CORROSION TEST In this test the reaction product was blended with aPennsylvania solvent-refined oil of Sayvolt Universal viscosity of 53seconds at 210 F.,

and a section of a-bearing containing a cadmium-silver alloy surface andweighing about 6 grams was added to this blend. The oil was heated to175 C, for 22 hours while a stream of air was bubbled against thesurface of the hearing. The loss in weight of the bearing during thistreatment measured the amount of corrosion that had taken place. Asample of the straight oil was subjected to the same test at the sametime, and the diflerence between the losses in weight of the two bearingsections demonstrated conclusively the eilectiveness of the reactionproducts contemplated herein as corrosion-inhibitors.

SOCONY-VACUUM TURBINE Tnsr Twenty-five cc. samples of a furfural-reflnedRodessa crude of Saybolt Universal viscosity of 150 seconds at 100 F.and of blends of this same oil and typical reaction products weresubjected to the following test to determine theefifectlveness of thereaction products contemplated by this invention as inhibitorsfor turbinoils: To ach sample were added 1 gram of iron granules and 24 inches of18 gauge copper wire. The samples were then heated to a temperature of200 F, with 5 liters of air per hour bubbling therethrough. Two cc. ofdistilled water were added each day. The results of the tests which weremade for color and acidity or neutralization number and amount ofsludgeformed after certain time intervals are OPERATION Test Todemonstrate the efiectiveness of the reaction products under actualoperating conditions of an automotive engine, unblended ollsand'improved oils, containing the reaction products, were subjected tothe Lauson engine test. The tests were carried out in a single-cylinderLauson engine operated continuously over a time interval of 16 hourswith the cooling medium held at a tem- It will be apparent from theforegoing test data that the reaction products of this invention areeffective not only to inhibit corrosion and the various effects ofoxidation upon mineral oils, such as formation of rust, sludge, colorbodies and other undesirable products, but also to depress the pourpoint.

The improved properties obtained and the degree of improvement effectedmay be varied with the aldehyde, polyamine, hydroxyaromatic compound,phosphorus halide or sulfide, and metal, if the latter is present.

The amount of improving agent used varies with the mineral oil orlubricating oil fraction with which it is blended and with theproperties desired in the final oil composition. These reaction productsmay be added to mineral oil in amounts of from about 0.01 to about 10percent, but amounts of from about 0.1 to about percent generallyprovide satisfactory improvement.

It is to be understood that although I have described certain preferredprocedures which may be followed in the preparation of the novelreaction products contemplated herein as multifunctional addition agentsfor mineral oils and have indicated representative reactants for use intheir preparation, such procedures and reactants are merely ilustrativeand the invention is not to be considered as limited thereto or therebybut includes within its scope such changes and modifications as fairlycome within the spirit of the appended claims.

I claim:

1. An improved mineral oil containing a minor proportion, sumcient toinhibit said oil against the deleterious effects of oxidation, of anoilsoluble, phosphorus-containing reaction product obtained by reactingone molar equivalent of an aldehyde with about one molar equivalent of ahydroxyaromatic compound and at least about one-half molar equivalent ofa polyamine in which each amino group has at least one hydrogen atom, inthe presence of an inert diluent, at a temperature falling within therange varying between about 20 C. and the reflux temperature of thediluent and for a time sufficient to effect condensation, to produce acondensation product, and reacting said product with about one molarequivalent of a phosphorus compound selected from the group consistingof a phosphorus halide, a phosphorus thiohalide and a phosphorussulfide, in the presence of an inert solvent, at a temperature fallingwithin the range varying between about 20 C. and the reflux temperatureof the inert solvent and for a time sufflcient to effect phosphorizationof said condensation product.

2. An improved mineral 011 containing a minor proportion, from about0.01 per cent to about per cent, of an oil-soluble,phosphorus-containing reaction product obtained by reacting one molarequivalent of an aldehyde with about one molar equivalent of ahydroxyaromatic compound and at least about one-half molar equivalent ofa polyamine in which each amino group has at least one hydrogen atom, inthe presence of an inert diluent, at a temperature falling within therange i arying between about 20 C. and the reflux temperature of thediluent and for a time sufficient to effect condensation, to produce acondensation product, and reacting said product with about one molarequivalent of a phosphorus compound selected from the group consistingof a phosphorus halide, a phosphorus thiohalide and a phosphorussulfide, in the presence of an inert solvent, at a temperature fallingwithin the range varying between about 20 C. and the reflux temperatureof the inert solvent and for a time sufficient to effect phosphorizationof said condensatlon product.

3. An improved mineral oil containing a minor proportion, sufficient toinhibit said oil against the deleterious effects of oxidation of anoilsoluble, phosphorus-containing reaction product obtained by reactingone molar equivalent of an aldehyde with about one molar equivalent of ahydroxyaromatic compound and at least about one-half molar equivalent ofa polyamine in which each amino group has at least one hydrogen atom, inthe presence of an inert diluent, at a temperature falling within therange varying between about 20 C. and the reflux temperature of thediluent and for a time sufllcient to effect condensation, to produce acondensation product, and reacting said product with about one molarequivalent of a phosphorus halide, in the presence of an inert solvent,at a temperature tlling within the range varying between about 20 C. andthe reflux temperature of the inert solvent and for a time suflicient toeffect phosphorization of said condensation product.

4. An improved mineral oil containing a minor proportion, sufficient toinhibit said oil against the deleterious effects of oxidation of anoilsoluble, phosphorus-containing reaction product obtained by reactingone molar equivalent of an aldehyde with about one molar equivalent of ahydroxyaromatic compound and at least about one-half molar equivalent ofa polyamine in which each amino group has at least one hydrogen atom, inthe presence of an inert diluent, at a temperature falling within therange varying between about 20" C. and the reflux temperature of thediluent and for a time suflicient to effect condensation, to produce acondensation product and reacting said product with about one molarequivalent of phosphorus trichloride, in the presence of an inertsolvent, at a temperature falling within the range varying between about20 C. and the reflux temperature of the inert solvent and for a timesufficient to effect phosphorization of said condensation product.

5. An improved mineral 011 containing a minor proportion, sufflcient toinhibit said oil against the deleterious effects of oxidation of anoilsoluble, phosphorus-containing reaction product obtained by reactingone molar equivalent of formaldehyde with a wax-phenol in sufficientamount to provide about one molar equivalent of the phenol substituentthereof and at least about one-half molar equivalent of a polyaminc inwhich each amino group has at least one hydrogen atom, in the presenceof an inert diluent, at a temperature falling within the range varyingbetween about 20 C. and the reflux temperature of the diluent and for atime sufficient to effect condensation, to produce a condensationproduct and reacting said product with about one molar equivalent ofphosphorus trichloride, in the presence of an inert solvent at atemperapolyamine in which each amino group has at least one hydrogenatom, in the presence of an inert diluent, at a temperature fallingwithin the range varying between about C. and the reflux temperature ofthe diluent and for a time suflicient to efiect condensation, to producea condensation product and reacting said product with about one molarequivalent of a phosphorus sulfide, in the presence of an inert solventat a temperature falling within the range varying between about 20" C.and the reflux temperature of the inert solvent and for a timesuiflcient to effect phosphorization and sulfurization ofsaidcondensation product.

7. An improved mineral oil containing a minor proportion, suflicient toinhibit said oil against the deleterious effects of oxidation of anoilsoluble, phosphorusand sulfur-containing reaction product obtained byreacting one molar equivalent of an aldehyde, with about one molarequivalent of a hydroxyaromatic compound and at least about one-halfmolar equivalent of a polyamine in which each amino group has at leastone hydrogen atom, in the presence of an inert diluent, at a temperaturefalling within the range varying between about 20 C. and the refluxtemperature of the diluent and for a time suflicient to efiectcondensation, to produce a condensation product and reacting saidproduct with about one molar equivalent of phosphorus pentasulflde, inthe presence of an inert solvent at a temperature falling within therange varying between about 20 C. and the reflux temperature of saidinert solvent and for a time sufflclent to efiect phosphorization andsulfurization of said condensation product.

8. An improved mineral 011 containing a minor proportion, sufiicient toinhibit said oil against the deleterious eflects of oxidation of an011-.

soluble, phosphorusand sulfur-containing reaction product obtained byreacting one molar equivalent of formaldehyde, with about one molarequivalent of dlamyl phenol and at least about one-half molar equivalentof ethylene diamine, in the presence of an inert diluent, at atemperature falling within the range varying between about 20 C. and thereflux temperature of the diluent and for a time suflicient to effectcondensation, to produce a condensation product and reacting saidproduct with about one molar equivalent of phosphorus pentasulflde, inthe presence of an inert solvent at a temperature falling within therange varying between about 20 C. and the reflux temperature of theinert solvent and for a time sufilcient to effect phosphorization andsulfurization of said condensation product.

9. An improved mineral oil containing a minor proportion, suflicient toinhibit said oil against the deleterious eifects of oxidation of anoilsoluble, metaland phosphorus-containing reaction product obtained byreacting one molar equivalent of an aldehyde, with about one molarequivalent of a hydroxyaromatic compound and at least about one-halfmolar equivalent of a polyamine in which each amino group has at leastone hydrogen atom, in the presence of an pound selected from the groupconsisting of a phosphorus halide, a phosphorus thiohalide and aphosphorus sulfide, inthe presence of an inert solvent at a temperature.falling within the range varying between about 20 -C. and the refluxtemperature of the inert solvent and for a time sumcient to effectphosphorization of said condensation product and introducing a metalinto the phosphorized reaction product so obtained.

10. An improved mineral oil containing a minor proportion, from about0.01 per cent to about 10 per cent, of an oil-soluble, metalandphosphoruscontaining reaction product obtained by reacting one molarequivalent of an aldehyde, with about one molar equivalent of ahydroxyaromatic compound and at least about one-half molar equivalent ofa polyamine in which each amino group has at least one hydrogen atom, inthe presence of an inert diluent, at a temperature falling with in therange varying between about 20 C, and the reflux temperature of thediluent and for a time suiflcient to effect condensation, to produce acondensation product, reacting said product with about one molarequivalent of a phosphorus compound selected from the group consistingof a phosphorus halide, a phosphorus thiohalide and I a phosphorussulfide, in the presence of an inert solvent at a temperature fallingwithin the range varying between about 20 C. and the reflux "temperatureof the inert solvent and for a time sufflcient to effect phosphorizationof said condensation product and introducing a metal into thephosphorized reaction product so obtained.

11. An improved mineral oil containing a minor proportion, suflicient toinhibit said oil against the deleterious effects of oxidation, of an oilsoluble, tinand phosphorous-containing reaction product obtained byreacting one molar equivalent of formaldehyde, with a wax-phenol in anamount sufficient to provide about one molar equivalent of the phenolsubstituent thereof and about one-half molar equivalent of ethylenediamine, in the presence of an inert diluent;

at a temperature falling within the range varying between about 20 C.and the reflux temperature of the diluent and for a timesuflicient toeffect condensation, to produce a condensation product, reacting saidproduct with phosphorus trichloride, in the presence of an inert solventat' a temperature falling within the range varying between about 20 C.and the reflux temperature of the inert solvent and for a timesufficient to effect phosphorization of said condensation prod uct, andintroducing a metal into the phosphorized reaction product so obtained.

12. An improved mineral oil containing a minor proportion, sufiicient toinhibit said oil against the deleterious eifects of oxidation, of anoilsoluble, phosphorusand sulfur-containing reaction product obtained byreacting one molar equivalent of an aldehyde with about one molarequivalent of a hydroxyaromatic compound and at least about one-halfmolar equivalent of a polyamine in which each amino group has at leastone hydrogenatom, at a temperature falling within the range varyingbetween about 20 C.

I and the reflux temperature of the diluent and for a time sufficient toeffect condensation, to produce a condensation product, reacting saidproduct with a phosphorus compound selected from the group consisting ofa phosphorus halide, a phosphorus thiohalide and a phosphorus sulfide,in the presence of an inert solvent at a temperature falling within therange varying between about 20 C. and the reflux temperature of theinert solvent and for a time sufficient to effect phosphorization ofsaid condensation product, then reacting the phosphorized condensationproduct with a sulfurizing material selected from the group consistingof elementary sulfur, a sulfur halide and a mixture thereof, under thesame reaction conditions employed in the phosphorization reaction toeffect sulfurization of the phosphorized condensation product.

13. An improved mineral oil containing a minor proportion, sufiicient toinhibit said oil against the deleterious effects of oxidation, of anoilsoluble. metal-, phosphorusand sulfur-containing reaction productobtained by reacting one molar equivalent of an aldehyde with about onemolar equivalent of a hydroxyaromaticcompound and at least aboutone-half molar equivalent of a polyamine in which each amino group hasat least one hydrogen atom, in the presence of an inert diluent, at atemperature falling within the range varying between about 20 C. and thereflux temperature of the diluent and for a time suflicicnt to effectcondensation, to produce a condensation product, reacting said productwith about one molar equivalent of a phosphorus compound selected fromthe group consisting of a PhOS'.

, 16 phorus halide, a phosphorus thiohalide and phosphorus sulfide, inthe presence of an inert solvent. at a temperature falling within therange varying between about 20 C. and the reflux temperature of theinert solvent and for a time sumcient to effect phosphorization of saidcondensation product, then reacting the phosphorized condensationproduct with a sulfurizing material selected from the group consistingof elementary sulfur, a sulfur halide and a mixture thereof. under thesame reaction conditions employed in the phosphorization reaction toeffect sulfurization of the phosphorized condensation product.

and introducing a metal into the phosphorized and sulfurized reactionproduct so obtained.

EDWARD A. OBERRIGHT.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,146,584 Llpkin Feb. 7, 19392,263,445 Reiif Nov. 18, 1941 2,279,218 Badertscher et al. Apr. 7, 19422,282,710 Dietrich May 12, 1942 2,322,379 McCleary June 22, 19432,334,594 Zimmer Nov. 16, 1943 2,336,006 Fuller Dec. 7, 1943 2,339,710Lincoln Jan. 18, 1944 2,340,036 Zimmer Jan. 25, 1944 2,353,192 Sargentet a1 July 11, 1944 2,361,957 Musselman Nov. 7, 1944 2,363,134 McClearyNov. 21, 1944

